Azo dyestuffs and process of preparation



Patented Jan. 13, 1931 INo Drawing.

UNITED STATES MENTS, 'ro NEWPORT oHEMIcAL CORPORATION, A coaronnrron or DELAWARE,

Azo DYE'sr rFs Am) 'rRooEss or rREPAaArfoN This invention relates to azo dyestuffs and to a process of preparing the same. The dyestuffs of this invention dye wool-in yellowish orange to reddish orange tints characterized by their good to light and to milling. v

It is accordingly an object of this invention to provide azo dyestufis for dyeing wool in clear orange shades varying from a yellowish orange to a reddish orange which are fast the following general structural formula:

n whereinR andR are benzene-nuclei, R

is a pyrazolone. group and R is a naphthol I "or naphthol sulfonic acid. The tetrazo components employed are prepared from 4.4- diamino-diphenyl-methanes which may be prepared vfrom an amine and formaldehyde in an acid; solution by the use of 1/ mole of formaldehyde to 1 mole of amine. See method of German Patent No. 70,402 or German Patent No. 53,937 The'yare'not the so-called anhydro bases prepared by the use of 1 mole of the amine to 'l mole of formaldehyde as in German Patents 83,544, 93,540, 95,600, 96,851 and 96,852.

The group R in the above formula is a pyrazolone group, the'aromatic nucleus of which may be substituted by such groups as halogen, methyl, alkoxy, sulfonicacids and the like. The group R in the above formula is a naphthol or a naphthol sulfonic acid.

By a variation in the use ofvthe above coupling components the'shade of the dyestufi maybe varied in general from a yellow,- ish orange to a reddish orange. 'j'To give'the dyestuff a proper solubility for dyeing-wool, there must be present in the molecule at least one acid group as for example, .an SO H group. The latter may be present on either ofthe coupling components or on the tetrazo component i fastness properties Application filed. ul 2, 71928. Serial in. 290,043.

. The diamino-diphenyl-methanes have most probably the" following general formula: 1

in which the hydrogen onthe ben z enerings maybe substituted by such; groups as methyl,

halogen, alkoxy, sulfonic acid groups and the like.

, l/Vithout limiting my invention to any particular procedure, the following exampleJin to illustrate my method in its preferred form,

which method produces a compound having the following structure: V

CHI

22.6 partsof.L4Gdiamino-2.2-dimethyl dition containing 24.5 parts of lg-naphtholl- PATE'Nr-jomen I DANIEL ZINNER, or scorn MILWAUKEE, WISCONSIN, Ass enoa, BYMnsNnAssIGN- 7 ISO which P s y Weight re givemwilliserve 7 acid (Nevill'e-Winthers acid), betaor'alphanaphthol is used, a much yellower shade of orange is obtained. If the first coupling component is substituted by other pyrazolones,

as for example, phenyl-methyl-pyrazolone or the pyrazolone madefrom a Xylidine sulfonic acid or an anisidine sulfonic acid the shade becomes a redder orange. In case a L Y-diamino-diphenyl-methane sulfonic acid is employed then the coupling components do not necessarily have to. have a sulfonic acid group on them. Other 4.4-diamino-diphenyl-methanes may be employed in the above manner toproducea variety of shades on wool fast to light and milling.

Below is a, table showing the variation in shades using varying coupling components on 4.4: diamino-22-dimethyl-diphenyl-methane.

Couplingcomponents Shade 1 (2 5 dichloro 4 sulfo phenyl 3 methyl 5 pyrazo-v lone.

1 (2 5 dichloro 4- sulfo phenyl 3 methyl 5 pyrazolone.

l (2 5 dichloro 4- sulfo phenyl 3 methyl 5 pyrazolone.

1 (2 5 fllchloro 4- sulfo phenyl 3 methyl 5 pyrazol-naphthol- 4 -su1tonic Reddish orange.

acid.

Beta naphthol Yellowish orange.

Alpha naphthol Yellowish orange.

2 naphthol 6 8 'Yellowish orange.

disulfonic acid.

lone.

1 (2 5 dichloro 4- sulfo phenyl 3 methyl 5 pyrazolone.

1 (2 5 dichloro -4- sulfo phenyl 3 methyl 5 pyrazolone.

l (2 5 dichloro 4'- sulfo phenyl 3 methyl 5 pyrazo;

lone.

1 (2: 5 dichloro 4; su1fo phenyl 3 methyl 5 pyrazolone.

1 (2 5 dichloro 4- sulfo phenyl 3 methyl 5 pyrazo- I lone. 1 (2 5 dichloro 4- sulfo phenyl 3 methyl- 5 pyrazo-. 10

ne. 1 (2"- 5 dichloro 4- lone. 1-phenyl-3-methyl-5 pyrazolone.

' 1 naphthol 2-naohtho1-3-6- disulfonic acid.

2 naphthol 6 sulfonic acid.

2 naphthol 7 sul- Ionic acid.

7 ui: ionicacid 1 2' amino 5 naphthOl 7 SillfOIllC acid.

2 benzoyl amino 5 naph ol 7 sulfonic acid.

2 amino. 8 naphthol 6 sulfonie acid.

l-naphthollssulfonic acid.

Reddi sh orange.

Reddish orange.

' Reddish orange.

Reddish-orange.

Reddish orange.

Reddish orange.

' Brown.

Reddish orange.

otherwisethan. necessitated by the prior art.

I claim as my invention: 1..The process ofpreparing azo dyestuffs, which comprises coupling-a tetrazotized 4, 4-

diami-no diphenyl methane body with a pynazolone body and with a naphthol body. 2,..As new articles of manufacture, azo dyes of the following: generalformula:

containing, at least one sulfonic acid group in themolecule, in which the hydrogen atoms" on the benzene ringsmay be substituted by alkyl, alkoxy, halogen, sulfonic groups and the like and in which. R is a pyrazolone body and R a naphthol body, which dyes in general dye wool in clear orange shades varying from. yellowish orange to reddish orange: and are fast to lightand milling.

3.As"new articles of manufacture, Inat'erialsdyed withthe dyestufls of claim 2.

4:. The processof preparing azo dyestuffs, which comprises coupling tetrazotized 1-4 diamino-2p- 2 dimethyl-diphenyl --methane with 1- (255 dichloroil sulfo-) phenyl -'3 methyl-5 pyraz0l'one, and a naphthol body.

5. As new articlesof manufacture, azo dyestufisj. having} most probably the following structural formula;

"with l-naphthol--sulfonic acid and a pyrazolone compound.

v r 8. As new articles of manufacture; azo dye- :stufis having most: probably the followlng structural formula: Y r a v' V OH- in which R is a pyrazolone body.

9; As new articles of manufacture, materials dyed With the dyestufi's of claim 8. i s 10. The process of preparing an azo dyestufi, which comprises coupling tetrazotized 4 4-diamino-2 -2-dimethyl-diphenyl-methane with 1- (2-5-dich10ro-4'-sulf0-) -phenyl- 3-methyl-5 pyrazolone, and. 1-naphthol-4- sulfonic acid. A

11. As a new article of manufacture, an azo clyestuffhavin most probably the following structural ormulai H- -H I CH soar 12. As new articles of manufacture, materials dyed with the dyestufl of claim 11.

In testimony whereof I have hereunto suby v scribed my name at Carrollville, Milwaukee 7 County, Wisconsin. 7

DANIEL ZINNER. 

